New strategy to the synthesis of (N → B) phenyl[N-alkyliminodiacetate-O,O′,N]boranes: The crystal structure of (N → B) phenyl[N-benzyliminodiacetate-O,O′,N]borane, (N → B)phenyl[N-(4-methyl)benzyliminodiacetate-O,O′,N]borane and (N → B) phenyl[N-phenacyliminodiacetate-O,O′,N]borane

A new, mild and friendly method for the synthesis of (N → B) phenyl[N-alkyliminodiacetate-O,O′,N]boranes 2–7 is reported. All compounds were identified by ¹H, ¹¹B, ¹³C NMR and their high resolution mass spectra (HRMS) are reported. The structure of the compounds 2, 4 and 5 were established by single crystal X-ray. Compounds 2 and 4 crystallized with two independent molecules 2A, 2B and 4A, 4B, respectively in the asymmetric unit. These molecular structures established the bicyclic structure showing a N → B bond length of 1.666 (2) Å for 2A, 1.675 (2) Å for 2B, 1.675 (3) Å for 4A, 1.663 (3) Å for 4B and 1.679 (2) Å for 5, as well as different torsion angles of the junction, 28.70 (2)° (C11–B1–N6–C17) for 2A, 21.50 (2)° (C11a–B1a–N6a–C17a) for 2B, 25.76 (0.26)° (C11–B1–N6–C17) for 4A, 21.96 (0.28)° (C11a–B1a–N6a–C17a) for 4B and −29.22 (0.20)° (C5–N1–B1–C13) for 5.     

Deamination process in the formation of a copper(II) complex with glutamic acid and a new ligand derived from guanidinoacetic acid: Synthesis,characterization, and molecular modeling studies

A deamination process was observed after copper(II) complexation reaction with guanidinoacetic (Gaa) and glutamic acids (Glu), forming the binuclear copper(II) complex K₂Cu₂C₁₆H₂₃N₇O₁₂ · 1/2H₂O (1), which was characterized by elemental analysis (CHN), spectroscopy methods (IR and EPR), powder X-ray diffraction, thermogravimetric analysis (TGA), and mass spectrometry. A new ligand, namely biguanide-1,5-diethanoate (Bge) (C₆H₉N₅O₄), was formed during complexation, probably due to the reaction between two Gaa species and the consequent release of a significant amount of ammonia, thus, characterizing the deamination process. In complex 1, Bge behaved as a tetradentated ligand, using its oxygen and nitrogen atoms as coordinating sites to both Cu(II) ions. In addition, Glu has coordinated to Cu(II) through its α-N and O atoms. Theoretical calculations of the cis–cis, cis–trans, and trans–trans isomers of 1, considering three prototropic forms of the Bge ligand, were carried out using semi-empirical quantum mechanics (PM3/d). DFT (B3LYP and B3P86) calculations of complex 1, in which a hydrogen atom replaced the side chain of Glu, were also carried out using the 6-31G(d) basis set and the LanL2DZ effective core potential for the transition metal. Based on experimental and theoretical data, we concluded that the trans–trans isomer of the binuclear copper(II) complex 1 should be the most stable, although the occurrence of other isomers, even if in minor quantities, should not be disregarded.     

Solid-state C NMR and molecular modeling studies of acetyl aleuritolic acid obtained from Croton cajucara Benth

Solid-state ¹³C nuclear magnetic resonance (¹³C NMR) with magic-angle spinning (MAS) and with cross-polarization and magic-angle spinning (CP/MAS) spectra, and differential scanning calorimetry (DSC) techniques were used to obtain structural data from a sample of acetyl aleuritolic acid (AAA) extracted from the stem bark of Croton cajucara Benth. (Euphorbiaceae) and recrystallized from acetone. Since solid-state ¹³C NMR results suggested the presence of more than one molecule in the unitary cell for the AAA, DSC analysis and molecular modeling calculations were used to access this possibility. The absence of phase transition peaks in the DSC spectra and the dimeric models of AAA simulated using the semi-empirical PM3 method are in agreement with that proposal.     

Enantioselective 1,4-conjugate addition of diethylzinc to (E)-alkenyl aryl ketones catalysed by Cu/DiPPAM complex

We report here the use of the DiPPAM-L1 ligand for copper-catalysed asymmetric conjugate addition (ACA) of diethylzinc to various (E)-alkenyl aryl ketones where the aryl ring is either a phenyl group substituted by nitro, chloro or methoxy groups or not substituted, or a naphthyl group. When the conjugate addition was performed in the greener AcOEt solvent with 1 or 2 mol % of Cu(OTf)₂/DiPPAM complex, moderate to good yields (45–83%) and high enantioselectivities (up to 98%) were reached.     

Innovation in a Continuous System of Distillation by Steam to Obtain Essential Oil from Persian Lime Juice (Citrus latifolia Tanaka)

The citrus industry is one of the most important economic areas within the global agricultural sector. Persian lime is commonly used to produce lime juice and essential oil, which are usually obtained by batch distillation. The aim of this work was to validate a patented continuous steam distillation process and to both physically and chemically characterize the volatile fractions of essential Persian lime oil. Prior to distillation, lime juice was obtained by pressing the lime fruit. Afterwards, the juice was subjected to a continuous steam distillation process by varying the ratio of distillate flow to feed flow (0.2, 0.4, and 0.6). The distillate oil fractions were characterized by measuring their density, optical rotation, and refractive index. Gas chromatography GC-FID was used to analyze the chemical compositions of the oil fractions. The process of continuous steam distillation presented high oil recovery efficiencies (up to 90%) and lower steam consumption compared to traditional batch process distillation since steam consumption ranged from 32 to 60% for different steam levels. Moreover, a reduction in process time was observed (from 8 to 4 h). The oil fractions obtained via continuous steam distillation differed significantly in their composition from the parent compounds and the fractions.     

Application of 4D-QSAR studies to a series of raloxifene analogs and design of potential selective estrogen receptor modulators

Four-dimensional quantitative structure-activity relationship (4D-QSAR) analysis was applied on a series of 54 2-arylbenzothiophene derivatives, synthesized by Grese and coworkers, based on raloxifene (an estrogen receptor-alpha antagonist), and evaluated as ERa ligands and as inhibitors of estrogen-stimulated proliferation of MCF-7 breast cancer cells. The conformations of each analogue, sampled from a molecular dynamics simulation, were placed in a grid cell lattice according to three trial alignments, considering two grid cell sizes (1.0 and 2.0 ?). The QSAR equations, generated by a combined scheme of genetic algorithms (GA) and partial least squares (PLS) regression, were evaluated by "leave-one-out" cross-validation, using a training set of 41 compounds. External validation was performed using a test set of 13 compounds. The obtained 4D-QSAR models are in agreement with the proposed mechanism of action for raloxifene. This study allowed a quantitative prediction of compounds' potency and supported the design of new raloxifene analogs.     

Effects of Sodium Butyrate on Cell Death Induced by Photodynamic Therapy in U373-MG and D54-MG Astrocytoma Cell Lines

The damage induced by end products of photodynamic therapy (PDT) in astrocytoma tumors leads to cytotoxicity and cell death. Chromatin modifiers such as sodium butyrate (NaB) induce several genes involved in apoptosis, among others. The PDT improvement was evaluated by the measurement of its effectiveness in the treatment of U373-MG and D54-MG astrocytoma cell lines exposed to NaB. Cells exposed to 80 μg mL⁻¹ of δ-aminolevulinic acid (ALA) as precursor of endogenous photosensitizer (PS), protoporphyrin IX (PpIX), induced 16.67% and 28.9% of mortality in U373-MG and D54-MG, respectively. The mortality increased to 70.62% and 96.7%, respectively, when U373-MG and D54-MG cells were exposed for 24 h to 8 m m NaB prior to ALA-induction. In this condition, re-expression of some genes related to apoptosis in U373-MG, and differentiation in D54-MG were induced. PpIX accumulation was higher than ALA-induction and the acetylation of histone H4 induced by NaB was verified by immunocytochemistry in both cells. It can be concluded that modified chromatin and genes induced by NaB increment the cellular death induced by PDT in astrocytoma cells using PpIX as endogenous PS.     

Use of Onion Waste as Fuel for the Generation of Bioelectricity

The enormous environmental problems that arise from organic waste have increased due to the significant population increase worldwide. Microbial fuel cells provide a novel solution for the use of waste as fuel for electricity generation. In this investigation, onion waste was used, and managed to generate maximum peaks of 4.459 ± 0.0608 mA and 0.991 ± 0.02 V of current and voltage, respectively. The conductivity values increased rapidly to 179,987 ± 2859 mS/cm, while the optimal pH in which the most significant current was generated was 6968 ± 0.286, and the ° Brix values decreased rapidly due to the degradation of organic matter. The microbial fuel cells showed a low internal resistance (154,389 ± 5228 Ω), with a power density of 595.69 ± 15.05 mW/cm² at a current density of 6.02 A/cm²; these values are higher than those reported by other authors in the literature. The diffractogram spectra of the onion debris from FTIR show a decrease in the most intense peaks, compared to the initial ones with the final ones. It was possible to identify the species Pseudomona eruginosa, Acinetobacter bereziniae, Stenotrophomonas maltophilia, and Yarrowia lipolytica adhered to the anode electrode at the end of the monitoring using the molecular technique.     

The effect of ICT and higher-order capabilities on the performance of Ibero-American SMEs

Computational and Mathematical Organization Theory - Information and communication technologies (ICT) has the ability to create value by enabling other firm capabilities. Based on the ICT-enabled...